Treatment of cellulosic textile materials and products thereof



tatented Jan. 2, 1951 TREATMENT OF CELLULOSIC TEXTILE MATERIALS ANDPRODUCTS THEREG F Linton A. l'luck, Jr., Norwalk, Conn., assignor toAmerican Cyanamid Company,

New York,

N. Y., a corporation of Maine No Drawing. Application November 10, 1947,Serial No. 785,188

16 Claims.

This invention relates to the treatment of cellulosic textile materialsand to the products thereof. Mo e articularly the invention is concernedwith the production of cellulosic textiles. specifically cotton fabrics,having improved properties (e. g., better resistance to creasing orwrinkling) by a process which comprises impregnating the textile with aparticular combination of impregnants within a definite range ofproportions of each. Conditions also are so maintained that the amountof combined impregnants which are retained by the textile is kept withindefinite limits.

Generally described, my process of improvin the properties of cotton andother cellulosic textiles comprises impregnating such textiles with ,acombination of (1) a curable (more particularly heat-curable) product ofpartial reaction of ingredients comprising melamine and formaldehyde, e.g., dimethylol melamine, trimethylol melamine, the heat-curable orthermosetting alkylated, specifically methylated, methylol melamines,etc., which partial reaction product is at least partly soluble andpreferably substant: ally completely soluble in Water, and (2) afilm-iorming, substantially water-insoluble, thermopastic product ofpolymerization of a polymerizable mass including a lower alkyl acrylate,e. g., methyl acrylate, ethyl acrylate, npropyl acrylate, isopropylacrylate, n-butyl acrylate, isobutyl acrylate, sec.-butyl acrylate,etc., or mixtures thereof with each other or with other monomers orpartial polymers which are copolymerizable therewith to yieldfilm-forming, substantially water-insoluble, thermoplastic copolymers orinterpolymers. The products of (l) and (2) should be used in a weightratio corresponding to form 1 to 3 parts of the latter for each part ofthe former. After the cellulosic textile material has been impregnatedwith the aforementioned combination of impregnants in any suitablemanner, but preferably by treating the textile material, as byimmersion, with a substantially homogeneous aqueous compositioncontaining the mixed impregnants in dispersed or other form, the partialreaction product of 1) is cured in situ in intimate contact with thepolymerization product of (2) to a substantially water-insoluble state.The total amount of the products of (1) and (2) that are applied to thecellulosic textile material is such that the finished textile containsfrom abouts to about 40%, more particularly from to 30%, by weight ofthe dry (net dry) textile, of a substantially washfast impregnantconsisting of the product of (1) III-139.4)

2 in a cured or substantially water-insoluble state and thesubstantially water-insoluble product of (2).

The treatment of cellulosic textile materials with a water-soluble,curable methylated methylol melamine heretofore has been known and isdescribed, for example, in Patent No. 2,339,203 of Harold W. Stieglerand Linton A. Fluck, Jr., issued January 11, 1944. It was also suggestedprior to my invention that textile materials, including cotton textiles,be impregnated with various thermoplastic materials, among whichpolymers of unsaturated aliphatic aldehydes and polymeric esters ofunsaturated aliphatic acids, e. g., polymeric methyl acrylate,specifically have been mentioned. In some cases it has been contendedthat such thermoplastic materials impart increased resistance tocreasing or wrinkling to the textile, but, at least in the case ofcotton fabrics or cloths, such contentions are inconsistent withavailable evidence. In general, a thermoplastic impregnant when appliedalone to a cellulosic textile material, specifically a cotton fabric, inamounts such as are employed in practicing my invention merely imparts apermanent non-spring finish to the fabric. There is no substantialimprovement, if any, in the resistance of the fabric to creasing orwrinkling, and in many cases the tendency of the treated fabric tocrease or wrinkle is even greater than that of the untreated fabric.

When cotton fabrics are impregnated with a water soluble, curablemethylated methylol melamine, e. g., in the form of an aqueous solution,and the treated fabric thereafter dried and heated to cure theimpregnant to a substantially water-insoluble condition, the resistanceof the fabric to shrinking and creasing is considerably increased.However, the tensile strength of the fabric is materially lowered bythis treatment, the percentage loss in tensile strength in some casesbeing as much as 35% or more of that of the original fabric.

The present invention is a solution to the problem of imparting a higherdegree of crease resistance to cotton textiles, and e pecially tomercerized cotton fabrics, than has been obtained with the priortreating agents and to effect this result while at the same timeobviating or minimizing losses in the tensile strength of the andspecifically cotton fabrics, can be rendered resistant to creasing andthe losses in tensile strength either obviated or materially lessened bytreating the fabric as briefly described in the first and secondparagraphs of this specification and more fully hereafter. In. general,the degree of crease resistance imparted to the fabric is greater thanthat obtained by using only a curable methylated methylol melamine orother curable, water-soluble or -dispersible product of partial reactionof ingredients comprising melamine and formaldehyde. This was whollyunexpected and unpredictable, since the thermoplastic polymerizationproduct alone does not impart markedcrease resistance, if any, to acotton fabric. It also was surprising and unexpected that thethermoplastic polymerization product would obviate or decrease the lossin 'tensile strength which'normally results when a cotton textile isimpregnated with a curable methylated methylol melamine, v or equivalentcurable product of partial reaction of ingredients comprising melamineand formaldehyde, and thereafter dried and cured, since from the knownproperties of thermoplastic polymers and copolymers it would not beexpected that such materials would co-act, physically or otherwise, withthe methylated methylol melamine or equivalent material so that theembrittlement of the textile, as evidenced by a decrease in its tensilestrength, would be obviated or minimized. v The impregnated cotton andother cellulosic textiles of my invention also are resistant toshrinking, as well as to wear and abrasion. The finish is durable and isnot removed by washing in water. The hand may be varied considerably,for example, by varying the kind and amount of thermoplastic modifieremployed and by variations in the impregnating and finishing operations.In some cases. it may be stiffer than that of fabrics containing a curedmethylated methylol melamine alone, which is a characteristic that isdesired in many types of cellulosic textiles.

The curable partial reaction products of ingredients comprising melamineand formaldehyde which are used in practicing my invention are at leastpartly soluble in water, the preferred reaction products being thosewhich are substantially completely soluble therein, either in the formof a true solution or a colloidal dispersion. Examples of melaminereaction products that may be employed are those which comprise one ormore polymethylol melamines, more particularly di-, tri-, tetra-,pentaor hexamethylol melamine or mixtures thereof. Such products may beproduced in known manner by effecting reaction under neutral or alkalineconditions between melamine and an aqueous solution of formaldehyde inthe ratio of 1 mol of the former to from 2 Lo 6 or more mols of thelatter. To avoid the formation of the crystalline material which haslower water-solubility and to obtain the amorphous product of higherwater solubility, the mass advantageously is maintained at a temperaturenot less than about 70 C. during the reaction.

In order to minimize polymerization of the monomer, it is usuallydesirable to keep the reaction temperature from exceeding about 90 C.

The curable, methylated or methyl alcoholreacted methylol melamines,moreparticularly methylated polymethylol melamines, are especiallysuitable for use in practicing my invention. They may be prepared, forexample, by effecting reaction under acidic conditions between apolymethylol melamine and methyl alcohol in the ratio of 1 mol of theformer to from 2 to 6 mols of the latter, depending upon the number ofmethylol groupings in the melamine derivative and the extent ofmethylation (or etherification) desired. The reaction is stopped beforethe product becomes hydrophobic, alkali is added in an amount at leastsufficient to neutralize the reaction mass, after which the mass isdehydrated under vacuum. Advantageously the methylated methylolmelamine, more particularly poly- (methoxymethyl) melamine, is preparedin a manner such as is disclosed and claimed in the copendingapplication of Herbert J. West and William .T. Watt, Serial No. 568,780,filed December 18,1944. now Patent No. 2,529,856. Such methylatedmethylol melamines are miscible with water in all proportions at roomtemperature and are stable on storage at F. for at least two weeks.

The thermoplastic polymerization products are prepared by known methods.Although a polymer of a lower alkyl (e. g., methyl, ethyl, propyl,tert.-butyl, amyl, etc.) ester of acrylic acid may be used as thethermoplastic modifier, I prefer to employ copolymers or interpolymersof such esters (or mixtures thereof) with a suitable proportion of oneor more other monomers which are compatible and copolymerizabletherewith to yield a water-insoluble, fllm-forming thermoplasticcopolymerization product which is flexible or pliable in film form.Illustrative examples of monomers which may be employed in theproduction of copolymers useful in practicing my invention are compoundsdifferent from the lower alkyl acrylate component and which contain asingle CH2=C grouping, for instance: the monovinyl compounds (bothaliphatic and armomatic), including the vinyl esters of saturatedaliphatic monocarboxylic acids (e. g., vinyl acetate, vinyl propionate,vinyl butyrate, etc); the monovinylsubstituted cyclic compounds, forinstance styrene and the various nuclearly substituted styrenes (e. g.,the monoand dimethyl styrenes, the chloro, fluoro and other halogenostyrenes, the cyano styrenes, etc.), a-p-dimethyl styrene (isopropenyltoluene) and other a-substituted, nuclearly substituted styrenes, vinylpyridines, vinyl thiophenes, vinyl fiuorenes, etc.; the vinyl andvinylidene halides, e. g., the chlorides, bromides and fluorides;acrylic acid, acrylonitrile and the amides of acrylic acid, e. g.,acrylamide and the N-monoand -di-alky1 acrylamides (e. g., N- methylacrylamide, N-diethylacrylamide, etc. alkacrylic compounds, includingthe acids, esters, nitriles and amides, e. g., methacrylic, ethacrylic,etc., acids, methacrylamide, ethacrylamide, etc., and the N-monoalkyland -dialkyl substitution products thereof, methacrylonitrile,ethacrylonitrile and other hydrocarbon-substituted acrylonitriles, themethyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, amyl, e.c., estersof methacrylic, ethacrylic, etc., acids; the allyl and methallyl estersof saturated monocarboxylic acids, e. g., allyl and methallyl acetates,propionates, laurates, etc.; and numerous other vinyl, vinylidene,acrylic and other compounds containing a single CH2=C grouping. In somecases compounds containing a plurality of CH2=C groups, e. g.,1,3-butadiene, may comprise the comonomer employed in forming thecopolymer. Suitable compounds of this class are those which, like1,3-butadiene, are compatible and copolymerizable with the lower alkylacrylate to yield a water-insoluble, film-forming thermoplasticcopolymerization product which is flexible or pliable in film form.

It will be understood, of course, by those skilled in the art that theparticular monomeric material which is employed in producing thecopolymer is so selected and is used in such a proportion with the loweralkyl acrylate, e. g., ethyl acrylate, as to obtain a film-formingmaterial which, when applied to the cellulosic textile in combinationwith the curable melamine-formaldehyde reaction product, will impart tothe treated textile the desired finish and hand.

Particularly good results have been obtained with copolymers of a loweralkyl acrylate, specifically ethyl acrylate, and styrene oracrylonitrfle. However, as has been mentioned previously, a polymerinstead of a copolymer of a lower alkyl acrylate may be used as thethermoplastic modifier. Thus, I may employ the product of polymerizationof a polymerizable mass containing, by weight, from 50 to 100% of alower alkyl acrylate, specifically ethyl acrylate, and from 50 to 0% ofa different monomer which is copolymerizable therewith and whichcontains a CH2=C grouping, specifically styrene or acrylonitrile. Insome cases the monomeric material which is copolymerized with themonomeric lower alkyl acrylate may constitut as much as 90% by weight ofthe mixture of monomers, but usually I employ a thermoplastic modifierobtained by polymerization of a mixture containing, by weight, from 70to 90% of the lower alkyl acrylate and from 30 to 10% of the othercopolymerizable monomer. I prefer to use copolymers of, by weight, from'70 to 90% of ethyl acrylate and from 30 to 10% of styrene oracrylonitrile. The polymers and copolymers used in practicing myinvention are either substantially water-insoluble per se or yieldsubstantially water-insoluble compositions when the reactive melaminederivative is cured in intimate contact with the polymer or copolymer.

The thermoplastic polymerization products may be prepared in anysuitable manner but advantageously are produced by emulsionpolymerization (or copolymerization) technique, for example as describedin the copending application of Edward. L. Kropa, Serial No. 636,279,now abandoned, .filed December 20, 1945, with particular reference tothe emulsion copolymerization of styrene and certain acrylic esters.

The "curable, methylated methylol melamine, more particularly methylatedpolymethylol melamine, or other curable partial reaction product ofingredients comprising melamine and formaldehyde and the thermoplasticpolymerization productare ordinarily, and preferably, applied to thecellulosic material in the form of an aqueous dis-- persion or emulsioncontaining the aforemen tionedingredients, e. g., in a concentration offrom 8 to 40%, more particularly from 10 to 30%,

by weight thereon The reactive melamine resin may be in dissolved stateand the thermoplastic modifier dispersed in the aqueous solution of thedissolved melamine resin. When the textile is impregnated with 100%, byweight of the dry' formaldehyde and to decrease the heating time, asuitable catalyst may be added to the aqueous dispersion. e. g., oxalicacid, acetic acid, phosphoric acid, diammonium hydrogen phosphate, ethylammonium phosphate, diammonium phthalate, ammonium chloride, zincchloride, and others which are known to be catalysts for ouring suchreaction products. The amount of catalyst may be varied as desired or asconditions may require, but ordinarily the catalyst is employed in anamount corresponding to from 0.5 to 5% by weight of the melaminederivative.

The curable methylated methylol melamine or other melamine derivative ofthe kinds aforementioned and thermoplastic polymerization product areemployed in the ratio of, by weight, 1 part of the former to from 1 to 3parts (preferably from 1 to 2 parts) of the latter. The thermoplasticmodifier must be used in a weight ratio which is at least equal to thatof the melamine derivative in order to obtain the results (e. g., bettercrease resistance, minimizing or obviating tensile strength losses,etc.) hereinbefore set forth. If a weight ratio of thermoplasticmodifier to melamine derivative materially above 3 to 1 be employed,-theimpregnated cloth is excessively weighted, usually has a non-drapey handand is not satisfactory for use in applications (e. g., in dresses andother clothing) where the weight and feeling to th touch are important.Good results are obtained by using the curable melamine derivative andthermoplastic modifier in a weight ratio of approximately 1 to 1. orwith a relatively small excess of the latter, e. g., up to 50% excess byweight of the thermoplastic additive.

The melamine derivative and thermoplastic polymerization product may beapplied to the cotton fabric or other cellulosic textile material invarious ways. For example, if the curable reaction product andthermoplastic modifier are applied in the form of an aqueous dispersion,the dry or substantially dry cellulosic fabric to be treated may beimmersed in the dispersion. and then passed through pressure rolls orpadders to secure uniform impregnation and a controlled removal of theexcess dispersion. The fabric or other textile, however, may beimpregnated by other methods, e. g., by spraying or by means of suitableboxes located on a mangle.

The term "aqueous dispersion as used generally herein with referencetothe aqueous composition containing the reactive melamine resin andthermoplastic modifier includes within its meaning aqueous dispersionsin which the reactive melamine resin is present either dissolved in theaqueous phase in the form of a true solution or colloidal dispersed inthe said phase.

The pick-up of aqueous dispersion by the cotton or other cellulosicmaterial being treated should be adjusted so that the finished textilewill contain from 8 to 40%, more particularly from 10 to 30%, by weightOf the dry textile, of the cured resin (e. g., cured methylated methylolmelamine) admixed with the particular thermoplastic modifier employed inthe ratio of, by weight, from 1 to 3 parts (preferably from 1 to 2parts) of the latter for each part of the former. The amount of aqueousdispersion picked up by the cellulosic textile, that is, the so-called"wet pick-up," may be varied as desired or as conditions may require andmay range, for example, from about 40 to about or more by weight of thedry textile depending, for example, upon the particular textile treated,method and conditions of treatment, concentration of solids inmethylated polymethylol melamine.

the impregnating bath, amount of solids and properties desired in thefinished textile, etc.

The wet, impregnated cotton fabric or' other cellulosic textile materialis then dried and cured. The drying and curing temperatures may bevaried considerably, but ordinarily temperatures within the range ofabout 200 F. to about 400 I".

' are employed. The impregnated fabric may be ployed) admixed with thethermoplastic poly-- merization product, e. g., polymeric ethyl acrylatea copolymer of ethyl acrylate and styrene or acrylonitrile, etc., to asubstantially water-insoluble condition. 'The drying and curingoperation is flexible and may be varied to suit ,the availableequipment. Continuous methods are preferred. However, drying and curingalso may be effected by framing the impregnated fabric to width, as on apin tenter, drying the framed fabric, batching it upon a shell and thenallowing it to stand hot for a period sumcient to complete the drying(if not entirely dried Previously) and to convert the solid impregnantin situ to a water-insoluble state. In some cases drying and curing for2 r 3 hours at 200 F. may be required. Heating the dried fabric for 1minute at 340 F. or for a shorter time at a higher temperature haseffectively water-insolubilized the impregnant.

The finishing treatment usually consists in washing the treated textile,e. g., in an aqueous 150'-190 F. solution containing. by weight, from0.1 to 0.2% of soapand 0.1% soda ash, followed by rinsing in hot waterat the same temperature, drying and then calendering either hot or cold.

The process of the present invention may be used in treating bothuncolored and colored goods. It is applicable to the treatment of bothbleached and unbleached cotton goods, as well as mercerized cottonfabrics. Surprisingly, the results are generally better, especially inplant operations, on mercerized, more particularly scoured andmercerized or bleached and mercerized, materials than on unmercerizedcotton textiles.

In order .that those skilled in the art better may understand how thepresent invention may be carried into effect, the following examples aregiven by way of illustration and not by way of limitation. All partsandpercentages are by weight.

The methylated methylol melamine used in all of the examples was asubstantially completely water-soluble, heat-curable or thermosettingThis material is prepared by the following process: One mol of melamineis mixed with 3.3 mol's of aqueous 37% formaldehyde previously adjustedto a pH of approximately 8.0, the temperature being raised to 70 C. andmaintained at this point until a clear solution is obtained. Thesolution powder is alkylated by admixture with twice its weight of 95%methanol containing 0.5% of oxalic acid crystals, based on the weight ofthe methylol melamine. The mixture is heated to 70 C. and held at thistemperature for approximately minutes, or

7 parts of the latter.

until a clear solution is obtained, whereupon it is immediatelyneutralized by the addition of suillcient sodium hydroxide solution toraise the pH to' approximately 9.0. The neutralized reaction mass isthen evaporated to 80% solids under reduced pressure so that thetemperature does not rise above C.

EXALCPLEI hydrogen phosphate (curing catalyst) and hexamethylenetetramine (buffering agent) in the ratio of about-30 parts of the.former to about 4 The bath was made by diluting with water a compositioncomprising about 80% methylated methylol melamine and 20% water. and theresulting product was then stirred into an emulsion ofthe polymerizationproduct.

Impregnation was carried out by soaking the fabric material for about Vminute in the bath and squeezing the impregnated fabric through a padderso that the amount of liquid impregnant retained by the fabric .(socalled "wet pick-up") was about 90% by weight of the dry fabric. Thesqueezed fabric was then heated for 6. minutes at 290 F. to dry thefabric and to cure the applied resinous composition, that is, curablemethylated methylol melamine admixed with the particular polymerizationproduct employed, to a substantially water-insoluble state.

The dried textile was then given a mild washing for 2 minutes in anaqueous 160 F. solution containing 0.1% soap and 0.1% sodiumbicarbonate, followed by thorough rinsing in water at 160 F. andsqueezing of the rinsed fabric. The

- rinsed'and squeezed fabric was then pressed dry on a flat bed electricpress.

The fabrics employed in this example were x 80 cotton percale andmercerized cotton twill. The bath compositions each contained 30% byweight of solids, of which 10% of the bath composition was methylatedmethylol melamine and 20% was a thermoplastic polymerization product.For purpose of comparison a bath containing 10% by weight of methylatedmethylol melamine and no thermoplastic additive was included in theseries of tests. The wet pick-up was about by weight of the dry fabric.The finished fabric contained about 27 by weight of the dry fabric, ofsolid, resinous impregnant of which A; was cured methylated methylolmelamine resin and 3:; was thermoplastic modifier. Tables I and 11 showthe thermoplastic materials employed and test data on the treated andlightly washed fabrics.

For purpose of comparison data also are given on the untreated fabrics.In these tables and in others which follow W" means 'warp" and F meansfilling. The total tensile strength (warp plus filling in pounds) isdetermined using the apparatus and method of the American Society forTesting Materials described under D-76-45.

Total T. B. Lpcrease Resistance (W plus F in cm.) in the tables refersto the total values of crease resistance of samples of the treatedfabrics out along the warp and along the weft, using the apparatus andprocedure developed by Tootal Broadhurt Lee Company. Ltd. (Manchester,England) and described in publications of this company. In this test,strips of fabric time the distance between theends of the sample ismeasured by means of a calibrated plane mir- EXAMPLE 2 Same as Example 1with the exception that the bath contained 22%% solids (736% methylatedmethylol melamine plus 15% of the thermoplastic modifier). The wetpick-up was about 90% by weight of the dry cloth. Table III shows thethermoplastic materials employed and test data on the treated andlightly washed fabrics.

Table [IL-80 a: 80 cotton parcels-7% methylated methulol melamine and15% thermoplastic modifier Tensile Total .Qg Loss Due 'r. B. L Test No.Thermoplastic Additive BtrgnFgtll; ggg mg, (Approx. (W lus F Percent) incm.)

Untreated cot- 91 3.6

ton percale. 10 raw m1 1: d20'7styre 68 25 11 opo ymero e y acry a eanne. 82 6.0 12 couplolymer 0180;, ethyl acrylate and 20% acryloni 88 3 6.6

ror mounted directly below the sample. The EXAMPLE 3 T. B. L.crease-resistance rating is the distance in centimeters between the endsof the sample after it has been subjected to the treatment describedabove. The total T. B. L. crease-resistance values reported in thetables are in each case the sum of the values obtained upon testing astrip of the fabric out along the warp and another strip out along theweft or filling.

Same as Example 1 with the exception that the bath contained 15% solids(5% methylated methylol melamine plus 10% of the thermoplasticmodifier). The wet pick-up was about 90% by 5 weight of the dry cloth.Table IV shows the thermoplastic modifiers employed and test data on thetreated and lightly washed fabrics.

Table I.-80 :c 80 cotton impale-40% methylated methylol melamine andthermoplastic modifier Tensile Total Loss '1. n. L. Tensm Due to CreaseTest No. Thermoplastic Additive Sa e n gh Treatment Resistance (Approx.(W plus F lbs) percent) in cm.

Untreated cotton 91 3. 6 perca e.

1-.-. None 69 24 5. 5 2 Copoiymer of 70% ethyl acrylate and styrene. 892 5. 7 3 Ctzpflolymer 0! 90% ethyl aerylate and 10% acryioni- 84 8 6.4

e. 4 Copolymer of 80% ethyl wylate and 20% aeryloni- 84 8 6. 9

r e. 5 Comiymer of ethyl acrylate and 30% acryloni- 84 8 6. 0

e. 6 Copol er of 79% ethyl acrylate and 21% dimethyl 88 3 6. 0

styrene.

Table II.-Mercerieed cotton twill-10 methylated methulol melamine and20% thermoplastic modifier Tensile Total ig fl Loss Due 'r. e. L. TestNo. Thermoplastic Additive su g n g g g' (Approx. plus F lbs) Percent)incm.)

Untreated mercerized 192 4 2 cotton twill. 7- None 153 20 6. 1 8Polymeric ethyl aerylate 174 9 8. 4 9 Copoiymer of ethyl acrylate and217% styl77 8 6. 4

rene.

Table IV.Mercerized cotton twlll-% metlwlated methylol melamine andthermoplastic modifier 'r I] 'r tal ggg o: '1. is. L. Test No.Thermoplastic Additive Strength g: gfi ifg @5 (Approx. (w plus FPercent) in cm Untreated mercerized 192 4.2

cotton twill. 13 None 166 14 5 4 14 Polymeric ethyl acrylate 104 1 a 5.915 Copolymer of 90% ethyl acrylate and 10% 178 7 ,1

' ene. 16 c p oiymer of 90% ethyl acrylate and 10% 188 2 5 gecrylonitrile.

Gain. V I

EXAMPLE 4 fabric is approximately the same as that of the Same asExample 1 with the exception that 20 untreated fabric- 5 impregnatingbaths comprising, by weight, 10% of methylated methylol melamine and10%, 15%, Same as Example 1 with the exception that im- 20% and of acopolymer of 80% ethyl acrylpregnating baths comprising, by weight, 10%oi.

ate and 20% acrylonitrile were used in treating 2 methylated methylolmelamine and 10%. 15% samples of 80 x 80 cotton percale. In addition and20% of a copolymer of 90% ethyl acrylate to the light wash of 2 minutesdescribed in Exand 10% of styrene were used in treating samples ample 1,the treated samples also were given a of 136 x 60 mercerized cottonbroadcloth. For l-hour wash using the same soap solution and purpose ofcomparison samples also were treated procedure except for the differenceintime. The by immersion in baths containing, by weight, resin solids inthe various baths are shown in 10% of methylated methylol melamine (withno Table V. The wet pick-up was about 90% by copolymer present), and10%, 15% and 20% of weight of the dry cloth. the same copolymer (with nomethylated methylol melamine present). The baths containing Table V'Resm solids bath methylated methylol melamine also contained a h t Th 1U A llllng accelerator of the kind and in the perfig gfi i as centagementioned under Example 1. The resin Test Mel solids in the variousbaths are shown in Table VII.

Per Cent Per Cent Description Table VII.Resm solids in bath 10 None. h l40 10 10 gg gfi gigghg g} acry ate Math lated Thermoplastic Additive 1015 D0. T t get I101 10 20 Do. (1mm 1o 25 Per Cent Per Cent DescriptionTable VI shows test data obtained on the None 10 ggg ethylacrylm treatedand washed samples. For purpose of None 15 1mg 10% sty comparison dataalso were given on the untreated None 20 10 10 Do. cotton percale. 10 15Do. Table VI Total Tensile Total T -B L Table VIII ShOWS test dataobtained on the W sltrellggthlb (g'leaie Rgsistanoe treated and washedsamples. For purpose of TestNm pus m pus mcm') comparison data also aregiven on a sample of Li ht 1 Hr Li ht Hr the untreated mercerizedbroadcloth which had 5 was}; i been immersed in water and dried prior totesting for tensile strength and crease resistance.

Untreated 80 x 80 cotton cal 93 94 3.2 3.3 Table VH1 38 $1 2-2 83 1a 6156:6 Total Tot 86 so 6.4 6.5 Tensile T. B. L. 88 86 Test No. Strength lesistance W Egg w plus F In all the foregoing examples each oi. thebaths m also contained a curing accelerator of the kind 05 U H t d 1% 60r d n and in the percentage mentioned under Exiks k and fi giff jlfi 126m ample 1. 22 2;;

When the thermoplastic modifiers mentioned 128 in Tables I to IV,inclusive, are employed alone in treating cotton percale or mercerizedcotton ms twill, that is, in the absence of methylated meth- 07 5.9 ylolmelamine but with other conditions the same as when the methylatedmethylol melamine alone From the results of the above tests it will beor with the thermoplastic modifier is used, the noted that thecombination of the thermoplastic total T. B. L. crease resistance of theimpregnated copolymer and methylated methylol melamine 13 provides atreated cloth having a materially improved crease resistance as comparedwith the untreated cloth and much better than that shown by cloths whichhave been treated with the a '14 treatment herein described also may beapplied to other textiles which are composed substantially or mainly ofcellulose or regenerated-celluloses, e. g., linen, hemp, jute, ramie,sisal, cellulose methylated methylol melamine alone or with acetaterayons, cellulose acetate-butyrate rayons, various percentages of thethermoplastic copclysaponified acetate rayons, viscose rayons, cuprammeralone. Furthermore, the combination of monium rayons, ethyl cellulose,etc., and mixtures treating agents yields a treated cloth having athereof with each other or with cotton. The higher tensile strength thanthat obtained by invention is particularly applicable to the treatusingmethylated methylol melamine alone. ment of cotton fabric material,specifically mer- Similar results are obtained when other 00- cerizedcotton cloth, and hence such textiles are polymers, e. g., copolymersof, by weight, 70-85% preferred for treating to improve theirproperethyl acrylate and 30-15% styrene, copolymers ties as hereinbeforedescribed. of, by weight, 70-90% ethyl acrylate and 30-10% Thermoplasticpolymerization products other acrylonitrile, etc., are substituted forthe particuthan those comprising polymers and copolymers larethylacrylate-styrene copolymer employed in of lower alkyl acrylates may becombined with a the above illustrative example. curable methylatedmethylol melamine or other Ex I I LE 6 curable product of partialreaction of ingredients Pounds comprising melamine and formaldehyde andthe resulting combination or admixture may be used Aqueous methylatedmethylol melamine in treating cotton or other cellulosic textile masmds)terials in a manner similar to that hereinbefore Emulsion of a copolymerof 90% ethyl acrylate and 10 styrene solids) 300 set forth. Examples ofsuch polymerization products are the polymers (or copolymers) obtainedCuring accelerator as in Example 1 2 water Sumcient to make 100 gallonsby polymerizing, alone or admixed 1th each other or with other monomers,the monomeric The above ingredients were mixed to yield an materialshereinbefore mentioned with particuimpregnflting b which had a D 0 Thislar reference to compounds that may be copolybath was used in a plantrun in treating four merized with a lower alkyl acrylate to yieldcodiiferent cellulosic fabric materials. The dry polymers suitable foruse in practicing the presfabrics were passed continuously at 48 yardsper ent invention. Such polymers and copolymers, minute through the bath(2 dips and 2 nips). however, are not equivalent, in the relationship inthe bath temperature being 80 F. The impregwhich they are used, to thepolymers and copolynated fabrics were dried in a pre-drier at 220 F.mers of the lower alkyl acrylates. and then in a tenter frame at 300 F.,followed The terms textile and "textile material" as by heating for 1minute at 340 F. to cure the used generally herein and in the appendedclaims methylated methylol melamine admixed with include within theirmeaning filaments, fibers, the ethyl acrylate-styrene copolymer to asubthreads, yarns, twisted yarns, etc., as such or stantiallywater-insoluble state. The fabrics in woven, felted or otherwise formedfabrics, were washed in 190 F. water containing 0.2% sheets, cloths andthe like. soap and 0.1% sodium carbonate, followed by I claim: rinsingin clear water at 190 P. All but a cotton 1. The process of improvingthe properties of cord fabric (cloth No. 4) were finished by drying acellulosic textile material which comprises imand cold calendering. Thewet pick-up of the pregnating the said textile material with a comcloths averaged of the dry weight of the 4b bination of (1) a curableproduct of partial reindividual cloth. The amount of resin (cured actionof ingredients comprising melamine and methylated methylol melamine pluscopolymer) formaldehyde, said product being at least partly on the goods(after drying and curing) averaged soluble in water,and (2) afilm-forming substance about 11.8% by weight of the dried fabric, ofconsisting essentially of a substantially waterwhich about 5% was curedmethylated methylol insoluble, thermoplastic product ofpolymerizamelamine and the remainder ethyl acrylatetion of polymerizablemonomers, said olymerizstyrene copolymer. able monomers consisting of,by weight, from 50% A description of the goods treated and the reto of alower alkyl acrylate and up to 50% sults obtained are given in Table IX.of a different monomeric compound containing Table IX Cloth No. l ClothN0. 2 Cloth No. 3 Cloth No. 4

Quantity treated 200yds 200yds 2fl0yds 3 0 yds. Descriptionandproperties oicloths. Bleached andmer- Bleachedand mer- Bleached only.Bleachedand mcrcenzed,

cerized. cerized. 3-ply cor Color Stripes Stripes Stripes Brown andwhite. Blue and white. 0 100% cotton 100% cotton Ravon blend"100%ootton. Filling do do 100% ootton- Do. PerI tcleit shrinkage ofuntreated 6.80 11.39 4.5.

0 Pgr centshrinkage of treated cloths 2.0 Tensile strength (in lbs.) oiun- 65143.4 741162-2- treated cloths (warp x filling). Tensile strength(in lbs.) of treated 66.2 x 42 4 69.2 x 250 60.0 x323.-." 77 x $2.5.

cloths (warp x filling). Total T. B. L. crease resistance of 5.2 4.8 5.36.0.

untreated cloths (W plus F in cm.) Total T. B. L. crease resistance of6.3 6.2 6.5 6.9.

treated cloths (W plus F in cm.) Hand and finish of treated cloths...G0od... Good Good Very good.

Although I have described my invention hereinbefore with particularreference to the treatment of cotton, specifically cotton fabrics, the

a CH2=C grouping and which is copolymerizable with said acrylate, theproducts of (1) and (2) being employed in a weight ratio corre- 15sponding to from 1 to 3 parts of the latter for each part of the former,and curing in situ the paitial reaction product of (1) in intimatecontact with the polymerization product of (2) to a substantiallywater-insoluble state, the amount of the products of (1) and (2) appliedto the said textilematerial being-such that the finished textilecontains from 8 to 40%, by weightof the dry textile, of a substantiallywashfast impregnant consisting of the product of (1) in cured state andthe product of (2).

2. A process as in claim 1 which includes the additional steps ofwashing the treated textile material in an aqueous soap-containingsolution followed by rinsing in water; drying the washed and rinsedtextile; and calendering thedried textile.

3. A process as in claim 1 wherein ethyl acrylate is the lower alkylacrylate.

4. A process as in claim 1 wherein the com-.

late and the remainder styrene.

5. A process as in claim 1 wherein the component of (2) is athermoplastic product of polymerization of a mixture of monomers ofwhich not less than 50% by weight thereof is ethyl acrylate and theremainder acrylonitrile.

6. The process of rendering cotton fabric material resistant to creasingwhich comprises impregnating said fabric material with from 1-0 to 30%,by weight of the dry fabric, of a mixture comprising (1) a curablemethylated methylol melamine and (2) a film-forming substance consistingessentially of a substantially water-insoluble, thermoplastic product ofpolymerization of polymerizable monomers consisting of, by weight, from50 to 100% of ethyl acrylate and up to 50% of styrene, the components of(1) and (2) being present in the said mixture in a weight ratiocorresponding to from 1 to 3 parts of the latter for each part of theformer, and the said mixture being applied to the said fabric materialin the form of a substantially homogeneous aqueous compositioncontaining the same, and thereafter drying the impregnated fabricmaterial and curing the methylated methylol melamine in the presence ofthe said polymerization product to a substantially water-insolublestate, thereby ob-' taining an impregnated cotton fabric materialcontaining a substantially washfast solid impregnant and which has ahigher tensile strength and a better crease resistance than the samecotton fabric material which has been similarly impregnated with anaqueous composition containing the same amount of the methylatedmethylol melamine of (1) but none of the thermoplastic material of (2)and thereafter has been similarly dried and cured.

7. A process as in claim 6 wherein the filmforming substance of (2) is acopolymer of monomers consisting of, by weight, from about 70% to about90% of ethyl acrylate and from about 30% to about 10% of styrene.

8. A process as in claim 6 wherein the methylated methylol melamine of(l) and the film-forming substance of (2) are present in the aqueouscomposition in a weight ratio corresponding to from 1 to 2 parts of thelatter for each part of the former, and the thermoplastic material of 2)is a copolymer of monomers consisting of, by weight, about 90% ethylacrylate and about 10% styrene.

9. A process as in claim 6 wherein the cotton fabric material is amercerlzed cotton cloth.

assapao 10. The process of rendering cellulosic fabric materialresistant to creasing which comprises impergnating said fabric materialwith from 10 to 30%. by weight of the dry fabric, of a mixturecomprising (1) a water-soluble methylated methylol melamine and (2) athermoplastic material which is a copolymer of monomers consisting of byweight, from about 70% to about of ethyl acrylate and from about 30% toabout 10% of styrene, the components of (1) and (2) being present in thesaid mixture in a weight ratio corresponding to from 1 to 2 parts of thelatter for each part of the former, and the said mixture being appliedto the said fabric material in the form M a substantially homogeneousaqueous composition containing the same, drying the impregnated fabricmaterial and thereafter heat-v ing thedried material at'a temperaturewithin the range of 250 F. to 400 F. to convert the said methylatedmethylol melamine admixed with the said copolymer to a'substantiallywater-insoluble condition.

11. A cellulosic textile material' which is resistant to creasing andwhich contains'from 8 to 40%, by weight of the dry textile material, ofa combination of (1) a substantially water-insoluble, curedproductwhich, prior to curing, is a curable product of partial reaction ofingredients comprising melamine and formaldehyde, said curable productbeing at least partly soluble in water, and (2) a film-forming substanceconsisting essentially of a substantially water-in oluble product ofpolymerization of polymerizable monomers, said polymerizable monomersconsisting of, by weight, from 50%to of a lower alkyl acrylate and up to50% of a different monomeric compound containing a CH2='C grouping andwhich is copolymerizable with said acrylate, the said polymerizationproduct being present in the combination thereof with the said curableproduct, before curing of the latter, in a weight ratio corresponding tofrom 1 to 3 parts of the former for each'part of the latter.

12. A cotton fabric material which is resistant to creasing and whichcontains from 10 to 30%, by weight of the dry fabric material, of acombination of (l) a substantially water-insoluble, cured product which,prior to curing, is a curable methylatedmethylol melamine and (2) afilmforming substance consisting essentially of a substantiallywater-insoluble, thermoplastic product of polymerization ofpolymerizable monomers, said polymerizable monomers consisting of, byweight, from 50 to 100% of ethyl acrylate and up to 50% of styrene.thesaid polymerization product being present in the combination thereofwith i the said curable methylated methylol melamine, before curing ofthe latter, in a weight ratio corresponding to from 1 to 3 parts thereoffor each part of the said curable methylated methylol melamine, and thesaid cotton fabric material from 10 to 30%, by weight of the dry fabricmaterial, of a combination of (1) a substantially water-insoluble, curedproduct which, prior to curing, is a water-soluble, curable methylatedmethyl melamine and (2) a thermoplastic material which is a copolymer ofmonomers consistin: of, by weight, from about 70% to about 90% asaaoaoof ethyl acrylate and from about 30% to about of styrene, the saidcopolymer being present in the combination thereof with the said curablemethylated methylol melamine, before curing of the latter, in a weightratio corresponding to from 1 to 2 parts thereof for each part of thesaid curable methylated methylol melamine, and the said cellulosicfabric material having a higher tensile strength and a better creaseresistance than the same cellulosic fabric material which has beensimilarly impregnated with the same amount of the same product of (l)but none of the thermoplastic material of (2).

14. A cellulosic fabric material which is resistant to creasing andwhich is impregnated with from about 10% to about 30%, by weight of thedry fabric material, of a combination of (1) a substantiallywater-insoluble, cured product which, prior to curing, is awater-soluble, curable methylated methylol melamine and (2) a copolymerof 90% ethyl acrylate and 10% styrene, the said copolymer being presentin the combination thereof with the said curable methylol melamine,before curing of the latter, in a weight ratio corresponding to from 1to 2 parts thereof for each part of the said curable methylated methylolmelamine, and the said cellulosic fabric material having a highertensile strength and a better crease resistance than the same celluloslcfabric material which has been similarly impregnated with the sameamount of the same product of (1) but none of the copolymer of (2).

15. The method of rendering a cotton-containing fabric materialresistant to shrinking and otherwise improving its properties whichcomprises immersing the material to be treated in an impregnating bathmaintained at a temperature of about 80 F., said bath having a pH ofabout 'I and being constituted of Emulsion ofa copolymer of ethylacrylate and 10% styrene (25% solids) Curing accelerator consistingessentially of a mixture of diammonium hydrogen ph osphate (curingcatalyst) and hexamethylene tetramine (buffering agent) in the ratio ofabout 30 parts of the former to about 4 parts of the latter 2 WaterSufiicient to make gallons adjusting the wet pick-up of the fabric sothat the amount of cured methylated methylol melamine plus theaforementioned copolymer of ethyl acrylate and styrene on the fabric(after drying and curing) averages about 11.8% by weight of the driedfabric, of which about 5% is cured methylated methylol melamine and theremainder ethyl acrylate-styrene copolymer; drying the wet impregnatedfabric at a temperature up to 300 F. followed by further heating at atemperature of 340 F. for a brief period to advance the cure of themethylated methylol melamine in situ to a substantially water-insolublestate; washing the resulting fabric in an aqueous soapcontainingsolution followed by rinsing in water; and drying the washed and rinsedfabric.

16. A method as in claim 15 which includes the additional step of coldcalendering the dried fabric.

LINTON A. FLUCK, JR-

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,187,383 Ludwig Jan. 16, 19402,339,203 Stiegler Jan. 11, 1944 2,378,365 Swain et al June 12, 19452,499,653 Kropa Mar. 7, 1950 Certificate of Correction Patent No.2,536,050 January 2, 1951 LINTON A. FLUGK, JR.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 1, line 38, for the Word form read from; column 2, line 26, fornon-spring read non-springy; column 4, line 37, for armomatic readaromatic; column 6, line 57, r'or colloidal read colloidally; column 11,line 17 r'or were read are; line 6 1, after all insert of; column 16,line 3, for impergnating read impregnating; line 73, for methyl readmcthylol; and that the said Letters Patent should be read as correctedabove, so that the same may conform to the record of the case in thePatent Oflice.

Signed and sealed this 27th day of March, A. D. 1951.

[smAt] THOMAS F. MURPHY,

Assistant Commissioner of Patents.

Certificate of Correction Patent No. 2,536,050 January 2, 1951 LINTON A.FLUGK, JR.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 1, line 38, for the Word form read from; column 2, line 26, fornon-spring read non-springy; column 4, line 37, for armomatic readaromatic; column 6, line 57, r'or colloidal read colloidally; column 11,line 17 r'or were read are; line 6 1, after all insert of; column 16,line 3, for impergnating read impregnating; line 73, for methyl readmcthylol; and that the said Letters Patent should be read as correctedabove, so that the same may conform to the record of the case in thePatent Oflice.

Signed and sealed this 27th day of March, A. D. 1951.

[smAt] THOMAS F. MURPHY,

Assistant Commissioner of Patents.

Certificate of Correction Patent No. 2,536,050 January 2, 1951 LINTON A.FLUCK, JR.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 1, line 38, for the Word form read from; column 2, line 26, for

non-spring read non spri ngy; column 42, line 37, for ar1no1natic" reaaromatw; column 6, hne 57, for colloidal read colloidal/Z1 column 11,hne

47, for were read are; hne 6%, after all 1nsert of; column 16, line 3,for

' line impergnating read impregnwtmg; 73, for methyl read mlethylol;

and that the said Letters Patent should be read as corrected the samemay conf he Patent above, so that orm to the record of the case in tOffice.

Signed and sealed this 27th day of March, A. D. 1951.

[SEAL] THOMAS F. MURPHY,

Assistant Commz'ssz'oner of Patents.

1. THE PROCESS OF IMPROVING THE PROPERTIES OF A CELLULOSIC TEXTILEMATERIAL WHICH COMPRISES IMPREGNATING THE SAID TEXTILE MATERIAL WITH ACOMBINATION OF (1) A CURABLE PRODUCT OF PARTIAL REACTION OF INGREDIENTSCOMPRISNG MELAMINE AND FORMALDEHYDE, SAID PRODUCT BEING AT LEAST PARTLYSOLUBLE IN WATER, AND (2) A FILM-FORMING SUBSTANCE CONSISTINGESSENTIALLY OF A SUBSTANTIALLY WATERINSOLUBLE, THERMOPLASTIC PRODUCT OFPOLYMERIZATION OF POLYMERIZABLE MONOMERS, SAID POLYMERIZABLE MONOMERSCONSISTING OF, BY WEIGHT, FROM 50% TO 100% OF A LOWER ALKYL ACRYLATE ANDUP TO 50% OF A DIFFERENT MONOMERIC COMPOUND CONTAINING A CH2=C< GROUPINGAND WHICH IS COPOLYMERIZABLE WITH SAID ACRYLATE, THE PRODUCTS OF (1) AND(2) BEING EMPLOYED IN A WEIGHT RATIO CORRESPONDING TO FROM 1 TO 3 PARTSOF THE LATTER FOR EACH PART OF THE FORMER, AND CURING IN SITU THEPARTIAL REACTION PRODUCT OF (1) IN INTIMATE CONTACT WITH THEPOLYMERIZATION PRODUCT OF (2) TO A SUBSTANTIALLY WATER-INSOLUBLE STATE,THE AMOUNT OF THE PRODUCTS OF (1) AND (2) APPLIED TO THE SAID TEXTILEMATERIAL BEING SUCH THAT THE FINISHED TEXTILE CONTAINS FROM 8 TO 40%, BYWEIGHT OF THE DRY TEXTILE, OF A SUBSTANTIALLY WASHFAST IMPREGNANTCONSISTING OF THE PRODUCT OF (1) IN CURED STATE AND THE PRODUCT OF (2).